New! View global litigation for patent families

US6114437A - Polycarbonate articles with photochromic properties - Google Patents

Polycarbonate articles with photochromic properties Download PDF

Info

Publication number
US6114437A
US6114437A US09018296 US1829698A US6114437A US 6114437 A US6114437 A US 6114437A US 09018296 US09018296 US 09018296 US 1829698 A US1829698 A US 1829698A US 6114437 A US6114437 A US 6114437A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
polycarbonate
resin
photochromic
aromatic
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US09018296
Inventor
Michael W. Brown
Douglas G. Hamilton
Rodney L. Michel
John G. Skabardonis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/205Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041Optical brightening agents, organic pigments
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2369/00Characterised by the use of polycarbonates; Derivatives of polycarbonates

Abstract

Polychromic articles are manufactured by solvent casting polycarbonate resins previously mixed with a photochromic dye and evaporating the solvent. The films produced can be insert injection molded with polycarbonate substrates to obtain photochromic articles.

Description

BACKGROUND OF THE INVENTION

The invention relates to polycarbonate resins and more particularly to polycarbonate resin molded articles. This invention further relates to polycarbonate resin molded articles comprising dyes, which may be photochromic, and/or metallic particles.

Polycarbonate is an amorphous, thermoplastic resin that has properties desirable for many articles. For example, glazings, lenses and automotive headlight lenses made of polycarbonate have high impact resistance and strength. Polycarbonate resin also can be highly transparent and has a desirably high refractive index. Furthermore, the thermal properties of polycarbonate resin makes the resin conducive to processing by conventional techniques, such as injection molding. However, there are also various shortcomings relating to polycarbonate articles. For example, no method presently exists for making high quality dyed or photochromic dyed polycarbonate articles such as glazings. Moreover, no method presently exists for making high quality polycarbonate articles that possess a metallic, or glitter appearance.

Two current methods of incorporating organic dyes into thermoplastic materials, such as polycarbonate, involve either inclusion of organic dye throughout the molded thermoplastic material or imbibition of dye into a surface of the thermoplastic material. Existing techniques, such as injection molding, for including organic dyes throughout thermoplastic materials, such as polycarbonate, typically do not yield satisfactory results. The unsatisfactory results occur for several reasons, including the relatively high temperatures required for satisfactory injection molding and the relatively high glass transition temperatures of polycarbonate. For example, photochromic dyes such as naphthopyrans, spironaphthopyrans, and spirooxazines that are co-melted with polycarbonate typically break down when exposed to the relatively high temperatures present during polymer melting. As another example, polycarbonate has a stiff molecular structure that is reflected by the relatively high glass transition temperature. Therefore, even in the absence of photochromic compound break down, the stiff molecular structure of polycarbonate substantially inhibits full activation of the photochromic dye, since the photochromic dye must go through a geometric transformation in the polycarbonate to activate.

Imbibition of dyes into surfaces of polycarbonate also yields unsatisfactory results, related to the relatively high glass transition temperatures of polycarbonate. It is thought that the stiff molecular structure prevents dye from penetrating the polycarbonate. Modification of the surface structure of polycarbonate resin by treatment with a solvent is said to improve imbibition of dyes into polycarbonate. U.S. Pat. No. 5,268,231 discloses that cyclohexanone is an effective solvent for modifying the polycarbonate surface structure to accept dyes. However, the method described leaves the surface of the polycarbonate with a rough, orange-peel type texture that is unacceptable for many purposes.

Approaches to manufacturing photochromic articles from thermoplastic resin materials and to avoid thermal degradation to the dye additive have also included molding of the articles by room temperature casting techniques; see for example the descriptions in U.S. Pat. Nos. 5,219,497 and 5,531,940. However, in many instances it is desirable to use thermal processing techniques.

The Japanese Patent Application No. 59-128192 filed Jun. 21, 1984 and laid open on Jan. 11, 1986 describes films with photochromic additives that are inserted into a mold following which the mold is filled (insert-injection molding). However, the films used (with photochromic properties) are prepared by imbibing, or coating a pre-formed film. The photochromic colorants are not homogeneously dispersed in the film and lack the quality of a homogeneous dispersion.

Approaches to manufacturing polycarbonate articles that have a metallic, or glitter appearance have thus far been largely unsuccessful because metallic additives cause degradation of polycarbonate at high temperatures. Moreover, relatively high loading of a metal is typically required to produce a metallic appearance, which exacerbates the degradation problem. It would be desirable to produce semi-transparent polycarbonate articles having a metallic appearance, but a relatively low metal loading, for applications such as sunglasses. It would also be desirable if such metallic polycarbonate articles were also photochromic.

The method of the present invention disperses homogeneously throughout a solvated polycarbonate resin, the dyes, which may be photochromic, and/or a metallic additive. The solvent mixture is then cast to form a film of polycarbonate having the dye and/or metallic additive homogeneously dispersed therein. The cast film can be placed in a mold against a mold wall and a substrate resin injected into the mold behind the insert. The article is thus molded without exposing the dye to high temperature for long periods of time, thus avoiding degradation of the dye.

SUMMARY OF THE INVENTION

The present invention comprises a process for the manufacture of a dyed and/or metallic polycarbonate resin blends and articles, which comprise;

dissolving a thermoplastic, aromatic polycarbonate resin in an organic solvent;

homogeneously mixing with the dissolved resin, an effective proportion of a photochromic dye, and/or an effective proportion of a metallic additive to impart a metallic appearance to the article and/or an effective proportion of a dye that is not photochromic;

casting a film of the mixture; and

removing the solvent.

The cast film can be inserted into a mold against a mold wall and insert-molded to a polycarbonate resin substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the generalized structures of Chromene and Spiroxazine photochromic dyes.

DETAILED DESCRIPTION OF THE INVENTION

The aromatic carbonate polymers useful in the invention are polycarbonates. The method of preparation of polycarbonates by interfacial polymerization are well known; see for example the details provided in the U.S. Pat. Nos. 3,028,365; 3,334,154; 3,275,601; 3,915,926; 3,030,331; 3,169,121; 3,027,814; and 4,188,314, all of which are incorporated herein by reference thereto.

In general, the method of interfacial polymerization comprises the reaction of a dihydric phenol with a carbonyl halide (the carbonate precursor).

Although the reaction conditions of the preparative processes may vary, several of the preferred processes typically involve dissolving or dispersing the diphenol reactants in aqueous caustic, adding the resulting mixture to a suitable water immiscible solvent medium and contacting the reactants with the carbonate precursor, such as phosgene, in the presence of a suitable catalyst and under controlled pH conditions. The most commonly used water immiscible solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene, and the like.

The catalyst employed accelerates the rate of polymerization of the dihydric phenol reactant with the carbonate precursor. Representative catalysts include but are not limited to tertiary amines such as triethylamine, quaternary phosphonium compounds, quaternary ammonium compounds, and the like. The preferred process for preparing polycarbonate resins of the invention comprises a phosgenation reaction. The temperature at which the phosgenation reaction proceeds may vary from below 0 C, to above 100 C. The phosgenation reaction preferably proceeds at temperatures of from room temperatures (25 C) to 50 C. Since the reaction is exothermic, the rate of phosgene addition may be used to control the reaction temperature. The amount of phosgene required will generally depend upon the amount of the dihydric phenol and the amount of any dicarboxylic acid also present.

The dihydric phenols employed are known, and the reactive groups are the two phenolic hydroxyl groups. Some of the dihydric phenols are represented by the general formula: ##STR1## wherein A is a divalent hydrocarbon radical containing from 1 to about 15 carbon atoms; a substituted divalent hydrocarbon radical containing from 1 to about 15 carbon atoms and substituent groups such as halogen; ##STR2## wherein each X is independently selected from the group consisting of hydrogen, halogen, and a monovalent hydrocarbon radical such as an alkyl group of from 1 to about 8 carbon atoms, an aryl group of from 6-18 carbon atoms, an aralkyl group of from 7 to about 14 carbon atoms, an alkaryl group of from 7 to about 14 carbon atoms, an alkoxy group of from 1 to about 8 carbon atoms, or an aryloxy group of from 6 to 18 carbon atoms; and wherein m is zero or 1 and n is an integer of from 0 to 5.

Typical of some of the dihydric phenols that can be employed in the practice of the present invention are bis-phenols such as (4-hydroxy-phenyl)methane, 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol-A), 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane; dihydric phenol ethers such as bis(4-hydroxyphenyl) ether, bis(3,5-dichloro-4-hydroxyphenyl) ether; dihydroxydiphenyls such as p,p'-dihydroxydiphenyl, 3,3'-dichloro-4,4'-dihydroxydiphenyl; dihydroxyaryl sulfones such as bis(4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, dihydroxybenzenes such as resorcinol, hydroquinone, halo- and alkyl-substituted dihydroxybenzenes such as 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene; and dihydroxydiphenyl sulfides and sulfoxides such as bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide and bis(3,5-dibromo-4-hydroxyphenyl) sulfoxide. A variety of additional dihydric phenols are available and are disclosed in U.S. Pat. Nos. 2,999,835; 3,028,365 and 3,153,008; all of which are incorporated herein by reference. It is, of course, possible to employ two or more different dihydric phenols or a combination of a dihydric phenol with glycol.

The carbonate precursor can be either a carbonyl halide, a diarylcarbonate or a bishaloformate. The carbonyl halides include carbonyl bromide, carbonyl chloride, and mixtures thereof. The bishaloformates include the bishaloformates of dihydric phenols such as bischloroformates of 2,2-bis(4-hydroxy-phenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, hydroquinone, and the like, or bishaloformates of glycols such as bishaloformates of ethylene glycol, and the like. While all of the above carbonate precursors are useful, carbonyl chloride, also known as phosgene, is preferred.

Also included within the scope of the present invention are the high molecular weight thermoplastic randomly branched polycarbonates. These randomly branched polycarbonates are prepared by coreacting a polyfunctional organic compound with the aforedescribed dihydric phenols and carbonate precursor. The polyfunctional organic compounds useful in making the branched polycarbonates are set forth in U.S. Pat. Nos. 3,635,895 and 4,001,184 which are incorporated herein by reference. These polyfunctional compounds are generally aromatic and contain at least three functional groups which are carboxyl, carboxylic anhydrides, phenols, haloformyls or mixtures thereof. Some nonlimiting examples of these polyfunctional aromatic compounds include 1,1,1-tri(4-hydroxyphenyl) ethane, trimellitic anhydride, trimellitic acid, trimellitoyl trichloride, 4-chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic anhydride, and the like. The preferred polyfunctional aromatic compounds are 1,1,1-tri(4-hydroxyphenyl)ethane, trimellitic anhydride or trimellitic acid or their haloformyl derivatives. Also included herein are blends of a linear polycarbonate and a branched polycarbonate.

The term "polycarbonate" as used herein is inclusive of copolyester-polycarbonates, i.e., resins which contain, in addition to recurring polycarbonate chain units of the formula: ##STR3## wherein D is a divalent aromatic radical of the dihydric phenol employed in the polymerization reaction, repeating or recurring carboxylate units, for example of the formula: ##STR4## wherein D is as defined above and R1 is as defined below.

The copolyester-polycarbonate resins are also prepared by interfacial polymerization technique, well known to those skilled in the art; see for example the U.S. Pat. Nos. 3,169,121 and 4,487,896.

In general the copolyester-polycarbonate resins are prepared as described above for the preparation of polycarbonate homopolymers, but by the added presence of a dicarboxylic acid (ester precursor) in the water immiscible solvent.

In general, any dicarboxylic acid conventionally used in the preparation of linear polyesters may be utilized in the preparation of the copolyester-carbonate resins of the instant invention. Generally, the dicarboxylic acids which may be utilized include the aliphatic dicarboxylic acids, the aromatic dicarboxylic acids, and the aliphatic-aromatic dicarboxylic acids. These acids are well known and are disclosed for example in U.S. Pat. No. 3,169,121 which is hereby incorporated herein by reference. Representative of such aromatic dicarboxylic acids are those represented by the general formula:

HOOC--R.sup.1 --COOH                                       (III)

wherein R1 represents an aromatic radical such as phenylene, naphthylene, biphenylene, substituted phenylene and the like; a divalent aliphatic-aromatic hydrocarbon radical such as an aralkyl or alkaryl radical; or two or more aromatic groups connected through non-aromatic linkages of the formula:

--E--

herein E is a divalent alkylene or alkylidene group. E may also consist of two or more alkylene or alkylidene groups, connected by a non-alkylene or alkylidene group, connected by a non-alkylene or non-alkylidene group, such as an aromatic linkage, a tertiary amino linkage, an ether linkage, a carbonyl linkage, a silicon-containing linkage, or by a sulfur-containing linkage such as sulfide, sulfoxide, sulfone and the like. In addition, E may be a cycloaliphatic group of five to seven carbon atoms, inclusive, (e.g. cyclopentyl, cyclohexyl), or a cycloalkylidene of five to seven carbon atoms, inclusive, such as cyclohexylidene; a sulfur-containing linkage, such as sulfide, sulfoxide or sulfone; an ether linkage; a carbonyl group; a direct bond; a tertiary nitrogen group; or a silicon-containing linkage such as silane or siloxy. Other groups which E may represent will occur to those skilled in the art. For purposes of the present invention, the aromatic dicarboxylic acids are preferred. Thus, in the preferred aromatic difunctional carboxylic acids, R1 is an aromatic radical such as phenylene, biphenylene, naphthylene, or substituted phenylene. Some non-limiting examples of suitable aromatic dicarboxylic acids which may be used in preparing the poly(ester-carbonate) or polyarylate resins of the instant invention include phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, o-, m-, and p-phenylenediacetic acid, and the polynuclear aromatic acids such as diphenyl dicarboxylic acid, and isomeric naphthalene dicarboxylic acids. The aromatics may be substituted with Y groups. Y may be an inorganic atom such as chlorine, bromine, fluorine and the like; an organic group such as the nitro group; an organic group such as alkyl; or an oxy group such as alkoxy, it being only necessary that Y be inert to and unaffected by the reactants and the reaction conditions. Particularly useful aromatic dicarboxylic acids are those represented by the general formula: ##STR5## wherein j is a positive whole integer having a value of from 0 to 4 inclusive; and each R3 is independently selected from the group consisting of alkyl radicals, preferably lower alkyl (1 to about 6 carbon atoms).

Mixtures of these dicarboxylic acids may be employed. Therefore, where the term dicarboxylic acid is used herein it is to be understood that this term includes mixtures of two or more dicarboxylic acids.

Most preferred as aromatic dicarboxylic acids are isophthalic acid, terephthalic acids, and mixtures thereof. A particularly useful difunctional carboxylic acid comprises a mixture of isophthalic acid and terephthalic acid wherein the weight ratio of terephthalic acid to isophthalic acid is in the range of from about 10:1 to about 0.2:9.8.

Rather than utilizing the dicarboxylic acid per se, it is possible, and sometimes even preferred, to employ the reactive derivatives of said acid. Illustrative of these reactive derivatives are the acid halides. The preferred acid halides are the acid dichlorides and the acid dibromides. Thus, for example instead of using isophthalic acid, terephthalic acid or mixtures thereof, it is possible to employ isophthaloyl dichloride, terephthaloyl dichloride, and mixtures thereof.

The proportions of reactants employed to prepare the copolyester-carbonate resins will vary in accordance with the proposed use of the product resin. Those skilled in the art are aware of useful proportions, as described in the U.S. patents referred to above. In general, the amount of the ester bonds may be from about 5 to about 90 mole percent, relative to the carbonate bonds. For example, 5 moles of bisphenol A reacting completely with 4 moles of isophthaloyl dichloride and 1 mole of phosgene would give a copolyester-carbonate of 80 mole percent ester bonds.

Any polycarbonate resin which is mold-injectable may be used as the substrate component to manufacture articles of the invention bearing a polycarbonate film containing a dispersion of the photochromic dyes. The preferred polycarbonate resin for injection molding is derived from bisphenol A and phosgene and having an intrinsic viscosity of about 0.3 to about 1.5 deciliters per gram in methylene chloride at 25.

The polycarbonate resin employed for admixture with the photochromic dye and cast to obtain the film for mold insertion is advantageously a relatively high molecular weight polyester-carbonate resin free of haze objections. These preferred resins for casting a film are derived from (i) at least one dihydric phenol, (ii) a carbonate precursor, and (iii) a minor amount of an aromatic ester precursor. The preferred aromatic ester precursor is selected from the group consisting of

isophthalic acid;

terephthalic acid;

isophthaloyl dichloride; and

terephthaloyl dichoride.

In the practice of the instant invention only one aromatic ester precursor is used or a mixture of two or more different ester precursors may be employed.

The amount of the aromatic ester precursor used in the preparation of the low haze carbonate polymers is an optical property improving amount. By optical property improving amount is meant an amount which is effective to improve the optical properties of the solvent cast films, i.e., effective to reduce the haze of said films. Generally this amount is from about 1 to about 10 mole percent, preferably from about 2 to about 9 mole percent, and more preferably from about 3 to about 8 mole percent. Mole percent of the aromatic ester precursor is based on the total amounts of said ester precursor and said dihydric phenol utilized in the preparation of the carbonate polymer.

Generally, if less than about one mole percent of said ester precursor is used there is no significant improvement in the optical properties of the film. If more than about 10 mole percent of said ester precursor is used the polymer begins to lose the advantageous properties exhibited by polycarbonate resins.

The instant high molecular weight solvent casting aromatic carbonate polymer contains recurring carbonate groups, carboxylate groups, and aromatic carbocyclic groups in the polymer chain in which at least some of the carbonate groups and at least some of the carboxylate groups are bonded directly to the ring carbon atoms of the aromatic carbocyclic groups.

The haze reduced carbonate polymers contain ester bonds and carbonate bonds in the polymer chain wherein the amount of the ester bonds is in the range of from about 1 to about 10 mole percent, preferably from about 2 to about 9 mole percent, and more preferably from about 3 to about 8 mole percent. For example, 5 moles of bisphenol-A reacting completely with 0-5 mole of isophthaloyl dichloride and 4.5 mole of phosgene would give a carbonate polymer of 10 mole percent ester bonds.

The haze reduced carbonate polymers contain at least the following two recurring structural units: ##STR6## wherein X, A, m, R3 and j are as defined herein-before.

Units VI are present in amounts of from about 1 to about 10 mole percent, based on the total amounts of units V and VI present, depending on the amounts of the aromatic ester precursor used.

The reduced haze high molecular weight thermoplastic aromatic carbonate polymers for mixing with the photochromic dyes generally have an intrinsic viscosity, as measured in methylene chloride at 25 C, of at least about 0.5 d/g, preferably at least about 0.6 d/g.

In accordance with the process of the present invention, the polycarbonate resin employed for cold-casting a film is first dissolved in an organic solvent. Any inert organic solvent may be used. An inert organic solvent is any that does not enter into reaction with the mixture components or adversely affects them. A preferred solvent is methylene chloride. A resin concentration in the organic solution is advantageously within the range of from about 1.0 to about 25 percent by weight.

To the polycarbonate resin solution, there is homogeneously mixed an effective proportion of a dye to impart color to a film and/or a photochromic effective proportion of a photochromic dye, and/or a proportion of a metallic additive that is effective to impart a metallic or glitter appearance to the film. An effective proportion of dye is generally within the range of from about 0.1 to about 10.0 percent by weight of the resin preferably 0.1 to 0.3%. An effective proportion of metallic additive is preferably 0.1 to 5.0% by weight of the resin. Mixing is carried out at room temperature.

The solvent cast films of the instant invention may be prepared by the conventional and well known solvent casting process which comprises pouring the solution into a template, and evaporating the solvent to form the film. Preferably evaporation is at room temperatures. These films generally have a thickness of from about 0.5 to about 25 mils, preferably from about 1 to about 15 mils.

Photochromic dyes are a well known class of compounds, as are methods of their preparation.

Examples of naphthopyran compounds suitable for imparting photochromic properties may be represented by formula (VII) as follows: ##STR7## wherein R4, R5, R6, R7, R8, R9, R10, and R11, respectively, may be hydrogen; a stable organic radical, such as alky], alkoxy, unsubstituted or substituted phenyl, naphthyl, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy; a heterocyclic group: halogen; a nitrogen-substituted group, such as amino or nitro; or a nitrogen-substituted ring compound, such as morpholino, piperidino, or piperazino; Z is hydrogen, a substituted phenyl group or a substituted naphthyl group; and V is hydrogen, a substituted phenyl group or a substituted naphthyl group, provided that at least one of Z and V is substituted phenyl or substituted naphthyl. The substituents of any phenyl or naphthyl group or groups at Z or V are selected from the following: a stable organic radical, such as alkyl, alkoxy, unsubstituted or substituted phenyl, naphthyl, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy; a heterocyclic group; halogen; a nitrogen-substituted group, such as amino or nitro; and a nitrogen-substituted ring compound, such as morpholino, piperidino, or piperazino; provided that at least one substituent of at least one substituted phenyl or substituted naphthyl at either A or B is phenyl, naphthyl or furyl.

Preferred naphthopyran compounds include 3-(4-biphenylyl) -3-phenyl-8-methoxy-3H-naphtho [2,1b]pyran, 3-(4-biphenylyl)-3-phenyl-3H-naphtho-[2,lb] pyran and 3,3-di(4-biphenylyl)-8-methoxy-3H-naphtho-[2,1b]pyran.

Examples of spironaphthopyran compounds may be represented by formula (VIII) as follows: ##STR8## wherein R1, R2, R5 R6, R7, R8, R9, and R10, respectively, may be hydrogen; a stable organic radical, such as alkyl, alkoxy, phenyl, naphthyl, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl, aroyloxy; a heterocyclic group; a halogen; a nitrogen-substituted group, such as amino or nitro; or a nitrogen-substituted ring compound, such as morpholino, piperidino, or piperazino; A is a substituted divalent aromatic radical. The substituents of the divalent aromatic radical may be hydrogen or a stable organic radical such as alkyl, alkoxy, phenyl, naphthyl, cycloalkyl, fury], alkoyl, alkoyloxy, aroyl, or aroyloxy. Additionally, the substituents of the substituted divalent may also be substituted with alkyl, alkoxy, phenyl, naphthyl, cycloalkyl, furyl, alkoyl, alkoyloxy, aroyl, or aroyloxy.

Preferred spironaphthopyran compounds for imparting photochromic effects include 8-methoxyspiro(3H- naphtho[2,1-b]pyran-3,9'-fluorene),spiro(3H-naphtho [2,1-b]pyran-3,9'-fluorene),8-methoxyspiro(3H-naphtho[2,1-b]pyran-3,1'-tetralone),6',7'-dimethoxy-8-methoxyspiro(3H-naphtho [2,1-b]pyran-3,1'-tetralone) 7'-methoxy-8-methoxyspiro(3H- naphtho[2,1-b]pyran 3,1'-tetralone), 2',3'-diphenyl-8-methoxyspiro(3H-naphtho[2,1-b]pyran-3,1'-tetralone) 2'-methyl-8-methoxyspiro(3H-naphtho [2,1-b]pyran-3,1'-tetralone), 2'-methyl-8-methoxy spiro(3H-naphtho(2,I-b]pyran-3,1'-indan), 2',3' diphenyl-8-methoxyspiro (3H-naphtho [2,1-b]pyran -3,1'-indene), 2',3'-diphenyl-8-methoxyspiro(3H- naphtho[2,1-b]pyran-3,1-tetralone), 2'-methyl-8-methoxyspiro(3H-naphtho[2,1-b]pyran-3,1-tetralone), 2'methyl-8-methoxyspiro(3H-naphtho[2,1-b]pyran-indan), and 2',3'-diphenyl-8-methoxyspiro(3H-naphtho[2,1-b]pyran-3,1'-indene).

Further details and methods for manufacturing the compound of formula (VIII) may be found in the U.S. Pat. Nos. 4,851,530 and 4,913,544, incorporated herein by reference thereto.

A number of photochromic dyes are commercially available from Keystone Aniline Company under the trivial names Reversocal Storm Purple, Plum Red, Berry Red, Corn Yellow, Oxford Blue and the like. Corn Yellow and Berry Red are Chromene compounds, while Storm Purple and Plum Red are Spirooxazics. The general structures of Chromene and Spirooxazene compounds are depicted in FIG. 1.

Preferred metallic additives suitable for use in the present compositions include metals, such as aluminum. Other nonmetallic reflective additives such as mica, may also be incorporated to provide a reflective material. It is preferred for the metallic additives to be powdered, and to have a particle size less than about 100 microns. The particles may be spherical or planar flakes. Suitable grades of aluminum particles are sold by the Silberline Corporation under the grades SSP-95020-C, SSP-504AR, ESS-800AR, and ESS-605AR. The properties of these grades are as follows:

              TABLE I______________________________________         Mean Particle Size  Grade D(50%) Shape______________________________________SSP-950-20-C  18 microns   flakes  SSF-504-AR 40 microns flakes  ESS-809-AR  8 microns spheres  ESS-604-AR 19 microns spheres______________________________________

Typically, an amount of a metallic particle is added which is sufficient to create a metallic appearance to the article, but is not sufficient to fully block transmission of light through the film. Preferred loading for aluminum particles range from 0.1 to 0.5% by weight. The "flake" shaped metallic particles are preferred because they require less loading to create the same degree of metallic appearance.

The mixing of the solvated compositions of the invention is done by solvent blending. The sequence of addition is not critical but all components should be thoroughly blended. Blending can be done continuously or batchwise. One or more photochromic dyes may be blended with the solvated polycarbonate resin.

The invention will be better understood with reference to the following examples, which are presented for purposes of illustration rather than for limitation, and which set forth the best mode contemplated for carrying out the invention.

The resin and dye and/or metallic particle blends of the invention may be further modified by the addition of other types of additives known to the art of plastics compounding. Such additives can include, for example, impact modifiers, other resins, plasticizers, flow promoters and other processing aids, stabilizers, mold release agents, ultraviolet screening agents and the like.

Preparation 1

A 1000 m four neck flask is fitted with a mechanical stirrer, a pH probe, aqueous caustic inlet tube and a Claisen adapter to which is attached a dry ice condenser and a gas inlet tube. To the flask are added 300 m water, 450 m methylene chloride, 0.7 m triethyl amine (0.005 mole) 57 g (0.25 mole) bisphenol-A, 0-24 g (0.0016 mole) 4-tertiarybutyl phenol, and 0.0125 mole (5 mole% based on bisphenol-A) of terephthaloyl dichloride. With stirring the pH is raised to 10 by the addition of 25% aqueous sodium hydroxide. Phosgene is introduced into the flask at the rate of 1 g/min for 30 minutes (0.3 mole) with the pH maintained at 10 to 11 by the use of said brine solution. The resin layer is separated from the brine layer, washed with 3 weight percent aqueous HC until the washing remains acidic, and twice with distilled water. The resin is then precipitated into 1500 m of methanol in a Waring blender and washed with 500 m more methanol and allowed to air dry.

This resin is then formed into a film by dissolving 5 g of this resin in 95 g of methylene chloride and pouring the solution into a 5 in.×10 in. stainless steel template resting on a glass plate. An inverted glass dish is loosely placed over the glass plate and the solvent is gradually evaporated.

Samples for % haze determination are cut from the center of the film. The % haze values are determined on a Gardner Pivotable-Sphere Hazemeter (Model HG-1204). The results are set forth in Table I, below.

Preparations 2-4

The procedure of Preparation 1, supra., is substantially repeated except that the 0.0125 mole of terephthaloyl dichloride is replaced with 0.0125 mole of other aromatic ester precursors as set forth in Table II, below.

The % haze of these films is determined and the results are set forth in Table II, below.

              TABLE II______________________________________              Mole %         % haze                                   thickness  Preparation Aromatic Ester Ester IV of of of  No. Precursor Precursor resin* film film______________________________________1       terephthaloyl              5        0.596 5.7   4 mils   dichloride  2 isophthaloyl 5 0.816 5.7 5 mils   dichloride  3 terephthalic 5 --** 22.7 5 mils   acid  4 isophthalic 5 0.959 5.0 4 mils   acid______________________________________ *Intrinsic Viscosity as determined at 25 C. in methylene chloride. **Insoluble in methylene chloride.
EXAMPLE 1

To 22.5 g of the resin obtained in the Preparation 1, supra., there is added with mixing 277.5 gm of methylene chloride (10% solution). To 150 gm of the solution there is added with stirring 0.0675 g of Berry Red photochromic dye (Keystone Aniline). The dye may be pre-dissolved in a suitable inert solvent such as butyl acetate; hexane; cyclohexane; various alcohols, including ethanol and methanol; and various ketones; such as cyclohexanone and methyl ethyl ketone. Approximately 6.0 g of the resulting mixture was cast into each of a series of 12 mm molds as described in Preparation 1 above and the solvent allowed to evaporate at room temperature, leaving a polycarbonate resin film with photochromic properties.

EXAMPLE 2

To 300 g of the solution obtained in the Example 1, supra., were added 0.15 g of Cyasorb 5411 (F528) (Cytec), 0.09 g Oxford Blue, 0.0225 g Berry Red and 0.0225 g Corn Yellow (all three photochromic dyestuffs obtained from Keystone Aniline) with mixing. Approximately 30 g of the resulting solution was cast into each of a series of 12 mm diameter molds and the solvent allowed to evaporate, leaving a polycarbonate resin film with photochromic behavior properties.

The photochromic films prepared in accordance with Examples 1-2, supra., are useful to prepare laminate photochromic articles by insert injection molding to adhere them to a lens substrate of polycarbonate resin. The technique of insert injection molding is well known; see for example the descriptions given in U.S. Pat. Nos. 4,898,706 and 4,961,894, both of which are incorporated herein by reference thereto. Advantageously, the molding is carried out by placement of the film insert into the front portion of the mold and the resin substrate is injected at a melt temperature within the range of about 450 F to 500 F.

The film insert may be pre-shaped using any suitable film shaping process.

Prior to molding the article in a molding machine, the film is placed against a recess of the mold plate before the mold halves are closed. The recess may be defined by a notch in the mold surface.

After placement of the film against the recesses, the molding machine is closed to form the mold. The thermoplastic resin is then injected into the cavities in the molten state to fill that portion of the cavities in the molten state to fill that portion of the cavities not occupied by the film and form the laminate article. After the injected resin solidifies, the cavity may be opened by moving the molding halves away from each other.

EXAMPLE 3

This example demonstrates formation of a laminate lens using the film produced in Example 1 to incorporate the photochromic property. The film portion is cut to match the mold shape and is placed against one surface of an open injection mold. The mold 20 halves are then closed. Molten Lexan® polycarbonate resin (General Electric Co., Pittsfield, Mass.) is injected into the mold cavity. The resin melt temperature of the machine is 575 F, and the mold temperature is 180° F.

After cooling, the mold halves are opened and the molded article ejected from the mold half. When tested, the article exhibited photochromic behavior.

EXAMPLE 4

This example demonstrates formation of a polycarbonate film that has a metallic, glittering appearance and incorporates photochromic dyes.

Four different films (A-D) were prepared by making a resin substantially according to Preparation 1, and mixing in the ingredients listed in Table II below to form a homogeneous resin mixture. The resin mixture was formed into a film by drying in a dish. The ingredients listed below are all described supra, with the exception of F528, which is a UV-absorber also known as Cyasorb 5411, available from Cytec.

The weight of each additive listed below in Table III is given in grams. Each experiment was performed by adding the additives to 24.4 g. of resin.

              TABLE III______________________________________Additive  A (grams) B (grams)                        C (grams)                                D (grams)______________________________________UV        0.0248    0.0248   0.0245  0.0241  F528  Dye  Oxford Blue 0.1099 0.1099 0.1100 0.1093  Purple 0.0122 0.0123 0.0125 0.122  Claret 0.0858 0.0855 0.0856 0.0854  Corn Yellow 0.248 0.245 0.0248 0.0247  AL Particles  SSP-950-20-C .0309  SSP-504-AR  0.0348  ESS-809-AR   0.0279  ESS-605-AR    0.0284______________________________________

Experiments A-D all contained the same weight of Aluminum pigment (0.1% by weight of resin), but different weights are shown in Table III because the different grades comprise varying amounts of a volatile carrier. Experiment A showed a very heavy metallic appearance, B showed a very fine metallic appearance, and C and D showed no metallic appearance. Therefore, the flake, shaped Aluminum particles provided a superior metallic appearance at lower loading levels.

Although the present invention has been described in considerable detail, with reference to certain preferred versions thereof, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to the descriptions of the preferred versions contain herein.

Claims (27)

What is claimed is:
1. A process for the manufacture of photochromic polycarbonate resin blends and articles, which comprises;
dissolving a thermoplastic, aromatic polycarbonate resin in an organic solvent to form a dissolved resin;
homogeneously mixing with the dissolved resin, a photochromic effective proportion of a photochromic dye;
casting a film of the mixture; and
removing the solvent.
2. The process of claim 1 wherein the polycarbonate resin is a solvent-castable polycarbonate reaction product of
(1) at least one dihydric phenol;
(ii) a carbonate precursor; and
(iii) an effective amount of an aromatic ester precursor to reduce haze.
3. The process of claim 2 wherein said amount of aromatic ester precursor is from about 1 to about 10 mole percent, based on the total amounts of said dihydric phenol and said aromatic ester pre-cursor used.
4. The process of claim 3 wherein said amount of said aromatic ester precursor is from about 2 to about 9 mole percent.
5. The process of claim 1 wherein said aromatic ester precursor is represented by the general formula ##STR9## wherein: R is independently selected from monovalent hydrocarbon radicals and halogen radicals;
X is independently selected from hydroxyl and halogen radicals;
n is a whole number from 0 to 4 inclusive; and
the --COX radicals are in the meta or para position relative to each other.
6. The process of claim 5, wherein said monovalent hydrocarbon radicals represented by R are selected from alkyl, cycloalkyl, aryl, aralkyl and alkaryl radicals.
7. The process of claim 6 wherein said monovalent hydrocarbon radicals represented by R are selected from alkyl radicals.
8. The process of claim 5 wherein said halogen radicals represented by R are selected from chlorine and bromine.
9. The process of claim 5 wherein n is zero.
10. The process of claim 5 wherein X is a hydroxyl radical.
11. The process of claim 10 wherein n is zero.
12. The process of claim 11 wherein said aromatic ester precursor is selected from isophthalic acid, terephthalic acid, and mixtures thereof.
13. The process of claim 5 wherein X is a halogen radical.
14. The process of claim 13 wherein said halogen radical is chlorine.
15. The process of claim 14 wherein n is zero.
16. The process of claim 15 wherein said aromatic ester precursor is selected from isophthaloyl di-chloride, terephthaloyl dichloride, and mixtures thereof.
17. The process of claim 2, wherein said carbonate precursor is phosgene.
18. The process of claim 17 wherein said dihydric phenol is bisphenol-A.
19. The process of claim 1 wherein the organic solvent is methylene chloride.
20. The process of claim 1 wherein mixing is at room temperature.
21. The film prepared by the process of claim 1.
22. The film of claim 21 insert injection molded to a polycarbonate resin substrate.
23. The article of the process of claim 22.
24. A process for the manufacture of thermoplastic film, which comprises:
dissolving a thermoplastic, aromatic polycarbonate resin in an organic solvent to form a dissolved resin;
homogeneously mixing with the dissolved resin an additive selected from the group consisting of: an amount of non-photochromic dye, an amount of photochromic dye, an amount of metallic particles, and combinations thereof;
casting a film of the mixtures; and
removing the solvent.
25. A process for the manufacture of thermoplastic film, which comprises:
dissolving a thermoplastic, aromatic polycarbonate resin in an organic solvent to form a dissolved resin;
homogeneously mixing with the dissolved resin an additive selected from the group consisting of: an amount of non-photochromic dye, an amount of photochromic dye, an amount of metallic particles, and combinations thereof;
casting a film of the mixtures; and
removing the solvent,
wherein the additive is an amount of metallic particles.
26. A process according to claim 25, wherein the metallic particles are flake shaped.
27. A process for the manufacture of thermoplastic film, which comprises:
dissolving a thermoplastic, aromatic polycarbonate resin in an organic solvent to form a dissolved resin;
homogeneously mixing with the dissolved resin a n additive selected from the group consisting of: an amount of non-photochromic dye, an amount of photochromic dye, an amount of metallic particles, and combinations thereof;
casting a film of the mixtures; and
removing the solvent,
wherein the additive is an amount of metallic particles together with a photochromic dye.
US09018296 1998-02-04 1998-02-04 Polycarbonate articles with photochromic properties Expired - Lifetime US6114437A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US09018296 US6114437A (en) 1998-02-04 1998-02-04 Polycarbonate articles with photochromic properties

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US09018296 US6114437A (en) 1998-02-04 1998-02-04 Polycarbonate articles with photochromic properties
CN 99100914 CN1198867C (en) 1998-02-04 1999-01-04 Polycarbonate articles with photochromic properties
EP19990300532 EP0934968B1 (en) 1998-02-04 1999-01-26 Polycarbonate articles with photochromic properties
EP20080151998 EP2025701A3 (en) 1998-02-04 1999-01-26 Polycarbonate articles with photochromic properties
DE1999640232 DE69940232D1 (en) 1998-02-04 1999-01-26 Polycarbonate articles having photochromic properties
JP2450999A JPH11315199A (en) 1998-02-04 1999-02-02 Photochromic polycarbonate product

Publications (1)

Publication Number Publication Date
US6114437A true US6114437A (en) 2000-09-05

Family

ID=21787228

Family Applications (1)

Application Number Title Priority Date Filing Date
US09018296 Expired - Lifetime US6114437A (en) 1998-02-04 1998-02-04 Polycarbonate articles with photochromic properties

Country Status (5)

Country Link
US (1) US6114437A (en)
EP (2) EP2025701A3 (en)
JP (1) JPH11315199A (en)
CN (1) CN1198867C (en)
DE (1) DE69940232D1 (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451236B1 (en) * 2000-02-02 2002-09-17 Gentex Optics, Inc. Method of making photochromic thermoplastics
US6948808B1 (en) * 2002-09-30 2005-09-27 Stylemark, Inc. Decorative eyeglass lens, method and related eyewear
US20070122626A1 (en) * 2003-09-09 2007-05-31 Vision-Ease Lens Photochromic Lens
US20070278815A1 (en) * 2006-06-02 2007-12-06 Wilfried Hedderich Photochromatic effect for polycarbonate glazing applications
DE102007002553A1 (en) 2007-01-17 2008-07-24 Bayer Materialscience Ag Photochromic material comprises a photochromic layer formed by three-dimensional radical polymerization between two polycarbonate layers
US20090130428A1 (en) * 2007-11-16 2009-05-21 Christian Dalloz Sunoptics Transparent optical substrate with elements distributed therein, method of producing and application of the same
US7829162B2 (en) 2006-08-29 2010-11-09 international imagining materials, inc Thermal transfer ribbon
WO2011082054A1 (en) 2009-12-30 2011-07-07 Sabic Innovative Plastics Ip B.V. Polycarbonate-poly(ether-ester) copolymer composition, method of manufacture, and articles therefrom
US8002935B2 (en) 2005-03-04 2011-08-23 Insight Equity A.P.X., L.P. Forming method for polymeric laminated wafers comprising different film materials
US8128224B2 (en) 2000-05-30 2012-03-06 Insight Equity A.P.X, Lp Injection molding of lens
US8298671B2 (en) 2003-09-09 2012-10-30 Insight Equity, A.P.X, LP Photochromic polyurethane laminate
US20130161844A1 (en) * 2011-12-27 2013-06-27 Norio TAKATORI Method for producing plastic lens
WO2016016808A1 (en) 2014-07-31 2016-02-04 Sabic Global Technologies B.V. Method of making plastic article
US9335443B2 (en) 2011-04-15 2016-05-10 Qspex Technologies, Inc. Anti-reflective lenses and methods for manufacturing the same
US9377564B2 (en) 2011-04-15 2016-06-28 Qspex Technologies, Inc. Anti-reflective lenses and methods for manufacturing the same
WO2016166619A1 (en) 2015-04-13 2016-10-20 Sabic Global Technologies, B.V. Photochromic spirooxazine compounds
US9522921B2 (en) 2015-04-13 2016-12-20 Sabic Global Technologies, B.V. Photochromic spirooxazine compounds
US9751268B2 (en) 2004-11-18 2017-09-05 Qspex Technologies, Inc. Molds and method of using the same for optical lenses

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070085234A1 (en) * 2005-10-19 2007-04-19 Boyle Timothy J Method and apparatus for solution casting film with secondary component
JP5302756B2 (en) * 2009-04-25 2013-10-02 三菱樹脂株式会社 Polyester film

Citations (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2999835A (en) * 1959-01-02 1961-09-12 Gen Electric Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same
US3027814A (en) * 1958-07-11 1962-04-03 Gottfried Wachtberger Vorm Eri Turbine blade copying machine
US3028365A (en) * 1953-10-16 1962-04-03 Bayer Ag Thermoplastic aromatic polycarbonates and their manufacture
US3030331A (en) * 1957-08-22 1962-04-17 Gen Electric Process for preparing copolyesters comprising reacting a carbonyl halide with a dicarboxylic acid and a dihydroxy compound in the presence of a tertiary amine
US3153008A (en) * 1955-07-05 1964-10-13 Gen Electric Aromatic carbonate resins and preparation thereof
US3169121A (en) * 1957-08-22 1965-02-09 Gen Electric Carbonate-carboxylate copolyesters of dihydric phenols and difunctional carboxylic acids
US3275601A (en) * 1956-01-04 1966-09-27 Bayer Ag Manufacture of polycarbonates using tertiary amines, quaternary amines and salts thereof as catalysts
US3334154A (en) * 1963-02-21 1967-08-01 Gen Electric Flame retardant mixed polycarbonate resins prepared from tetrabromo bisphenol-a
US3635395A (en) * 1970-01-16 1972-01-18 Melland Gear And Instr Co Inc Planetary conversion counter
US3915926A (en) * 1972-03-10 1975-10-28 Gen Electric Flame retardant thermoplastic compositions
JPS5122687A (en) * 1974-08-20 1976-02-23 Asahi Chemical Ind Hotokuromitsukusoseibutsu
US4001184A (en) * 1975-03-31 1977-01-04 General Electric Company Process for preparing a branched polycarbonate
US4035527A (en) * 1974-11-29 1977-07-12 American Optical Corporation Method of providing a phototropic layer on a carrier
US4188314A (en) * 1976-12-14 1980-02-12 General Electric Company Shaped article obtained from a carbonate-polyester composition
US4268134A (en) * 1979-03-07 1981-05-19 Corning Glass Works Lightweight laminated photochromic lenses
US4374931A (en) * 1982-01-08 1983-02-22 Corning Glass Works Photochromic glass suitable for ophthalmic applications
US4487896A (en) * 1983-09-02 1984-12-11 General Electric Company Copolyester-carbonate compositions exhibiting improved processability
JPS615910A (en) * 1984-06-21 1986-01-11 Mitsubishi Gas Chem Co Inc Preparation of synthetic resin formed piece excellent in photochromism
US4612362A (en) * 1985-03-27 1986-09-16 Allied Corporation Thermotropic polyester-carbonates containing 2,2-dimethyl-1,3-propanediol
JPH01156739A (en) * 1987-12-15 1989-06-20 Citizen Watch Co Ltd Organic photochromic sensitive body
US4851530A (en) * 1986-11-21 1989-07-25 Pilkington Plc Spiro-oxazine compounds
US4883548A (en) * 1987-04-24 1989-11-28 Hoya Corporation Process for producing laminated ophthalmic lens
US4898706A (en) * 1987-10-07 1990-02-06 Mitsubishi Gas Chemical Company, Inc. Process for producing molded articles with uneven pattern
US4913544A (en) * 1986-05-01 1990-04-03 Pilkington Plc Photochromic articles
US4961894A (en) * 1987-10-13 1990-10-09 Mitsubishi Gas Chemical Company, Inc. Process for producing synthetic resin molded articles
WO1992013927A1 (en) * 1991-02-06 1992-08-20 Battelle Memorial Institute Capped photochromic silver compositions for incorporation into a plastic matrix
US5219497A (en) * 1987-10-30 1993-06-15 Innotech, Inc. Method for manufacturing lenses using thin coatings
US5268231A (en) * 1991-07-02 1993-12-07 General Electric Company Method for the treatment of surfaces
US5531940A (en) * 1993-12-10 1996-07-02 Innotech, Inc. Method for manufacturing photochromic lenses
WO1996027496A1 (en) * 1995-03-03 1996-09-12 Bmc Industries, Inc. Production of optical elements
US5673251A (en) * 1995-01-31 1997-09-30 Pioneer Electronic Corporation Two substrates bonding type optical disk and method of producing the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3635895A (en) 1965-09-01 1972-01-18 Gen Electric Process for preparing thermoplastic polycarbonates
JPH0238516B2 (en) 1983-01-07 1990-08-30 Kato Seisakusho Kk Jibusochi
DE4304488C1 (en) * 1993-02-15 1994-06-01 Heinz Jakob Prodn. of photochromic plastics moulding useful e.g. for sunglass lens, visor, car window etc. - by impregnating granulate with photochromic dyestuff soln., drying and moulding

Patent Citations (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3028365A (en) * 1953-10-16 1962-04-03 Bayer Ag Thermoplastic aromatic polycarbonates and their manufacture
US3153008A (en) * 1955-07-05 1964-10-13 Gen Electric Aromatic carbonate resins and preparation thereof
US3275601A (en) * 1956-01-04 1966-09-27 Bayer Ag Manufacture of polycarbonates using tertiary amines, quaternary amines and salts thereof as catalysts
US3030331A (en) * 1957-08-22 1962-04-17 Gen Electric Process for preparing copolyesters comprising reacting a carbonyl halide with a dicarboxylic acid and a dihydroxy compound in the presence of a tertiary amine
US3169121A (en) * 1957-08-22 1965-02-09 Gen Electric Carbonate-carboxylate copolyesters of dihydric phenols and difunctional carboxylic acids
US3027814A (en) * 1958-07-11 1962-04-03 Gottfried Wachtberger Vorm Eri Turbine blade copying machine
US2999835A (en) * 1959-01-02 1961-09-12 Gen Electric Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same
US3334154A (en) * 1963-02-21 1967-08-01 Gen Electric Flame retardant mixed polycarbonate resins prepared from tetrabromo bisphenol-a
US3635395A (en) * 1970-01-16 1972-01-18 Melland Gear And Instr Co Inc Planetary conversion counter
US3915926A (en) * 1972-03-10 1975-10-28 Gen Electric Flame retardant thermoplastic compositions
JPS5122687A (en) * 1974-08-20 1976-02-23 Asahi Chemical Ind Hotokuromitsukusoseibutsu
US4035527A (en) * 1974-11-29 1977-07-12 American Optical Corporation Method of providing a phototropic layer on a carrier
US4001184A (en) * 1975-03-31 1977-01-04 General Electric Company Process for preparing a branched polycarbonate
US4188314A (en) * 1976-12-14 1980-02-12 General Electric Company Shaped article obtained from a carbonate-polyester composition
US4268134A (en) * 1979-03-07 1981-05-19 Corning Glass Works Lightweight laminated photochromic lenses
US4374931A (en) * 1982-01-08 1983-02-22 Corning Glass Works Photochromic glass suitable for ophthalmic applications
US4487896A (en) * 1983-09-02 1984-12-11 General Electric Company Copolyester-carbonate compositions exhibiting improved processability
JPS615910A (en) * 1984-06-21 1986-01-11 Mitsubishi Gas Chem Co Inc Preparation of synthetic resin formed piece excellent in photochromism
US4612362A (en) * 1985-03-27 1986-09-16 Allied Corporation Thermotropic polyester-carbonates containing 2,2-dimethyl-1,3-propanediol
US4913544A (en) * 1986-05-01 1990-04-03 Pilkington Plc Photochromic articles
US4851530A (en) * 1986-11-21 1989-07-25 Pilkington Plc Spiro-oxazine compounds
US4883548A (en) * 1987-04-24 1989-11-28 Hoya Corporation Process for producing laminated ophthalmic lens
US4898706A (en) * 1987-10-07 1990-02-06 Mitsubishi Gas Chemical Company, Inc. Process for producing molded articles with uneven pattern
US4961894A (en) * 1987-10-13 1990-10-09 Mitsubishi Gas Chemical Company, Inc. Process for producing synthetic resin molded articles
US5219497A (en) * 1987-10-30 1993-06-15 Innotech, Inc. Method for manufacturing lenses using thin coatings
JPH01156739A (en) * 1987-12-15 1989-06-20 Citizen Watch Co Ltd Organic photochromic sensitive body
WO1992013927A1 (en) * 1991-02-06 1992-08-20 Battelle Memorial Institute Capped photochromic silver compositions for incorporation into a plastic matrix
US5252450A (en) * 1991-02-06 1993-10-12 Battelle Memorial Institute Capped photochromic silver halides for incorporation into a plastic matrix
US5268231A (en) * 1991-07-02 1993-12-07 General Electric Company Method for the treatment of surfaces
US5531940A (en) * 1993-12-10 1996-07-02 Innotech, Inc. Method for manufacturing photochromic lenses
US5673251A (en) * 1995-01-31 1997-09-30 Pioneer Electronic Corporation Two substrates bonding type optical disk and method of producing the same
WO1996027496A1 (en) * 1995-03-03 1996-09-12 Bmc Industries, Inc. Production of optical elements

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
European Search Report for Application No. EP 99 30 0532. *

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451236B1 (en) * 2000-02-02 2002-09-17 Gentex Optics, Inc. Method of making photochromic thermoplastics
US8128224B2 (en) 2000-05-30 2012-03-06 Insight Equity A.P.X, Lp Injection molding of lens
US6948808B1 (en) * 2002-09-30 2005-09-27 Stylemark, Inc. Decorative eyeglass lens, method and related eyewear
US7858001B2 (en) 2003-09-09 2010-12-28 Insight Equity A.P.X., L.P. Photochromic lens
US8906183B2 (en) 2003-09-09 2014-12-09 Insight Equity A.P.X, Lp Photochromic polyurethane laminate
US8367211B2 (en) 2003-09-09 2013-02-05 Insight Equity A.P.X, L.P. Photochromic lens
US8298671B2 (en) 2003-09-09 2012-10-30 Insight Equity, A.P.X, LP Photochromic polyurethane laminate
US20070122626A1 (en) * 2003-09-09 2007-05-31 Vision-Ease Lens Photochromic Lens
US9751268B2 (en) 2004-11-18 2017-09-05 Qspex Technologies, Inc. Molds and method of using the same for optical lenses
US8002935B2 (en) 2005-03-04 2011-08-23 Insight Equity A.P.X., L.P. Forming method for polymeric laminated wafers comprising different film materials
US8440044B2 (en) 2005-03-04 2013-05-14 Insight Equity A.P.X., L.P. Forming method for polymeric laminated wafers comprising different film materials
WO2007143359A1 (en) * 2006-06-02 2007-12-13 Exatec, Llc Photochromatic effect for polycarbonate glazing applications
US7573630B2 (en) 2006-06-02 2009-08-11 Exatec, Llc Photochromatic effect for polycarbonate glazing applications
US20070278815A1 (en) * 2006-06-02 2007-12-06 Wilfried Hedderich Photochromatic effect for polycarbonate glazing applications
US7829162B2 (en) 2006-08-29 2010-11-09 international imagining materials, inc Thermal transfer ribbon
DE102007002553A1 (en) 2007-01-17 2008-07-24 Bayer Materialscience Ag Photochromic material comprises a photochromic layer formed by three-dimensional radical polymerization between two polycarbonate layers
US20090130428A1 (en) * 2007-11-16 2009-05-21 Christian Dalloz Sunoptics Transparent optical substrate with elements distributed therein, method of producing and application of the same
WO2011082054A1 (en) 2009-12-30 2011-07-07 Sabic Innovative Plastics Ip B.V. Polycarbonate-poly(ether-ester) copolymer composition, method of manufacture, and articles therefrom
US9335443B2 (en) 2011-04-15 2016-05-10 Qspex Technologies, Inc. Anti-reflective lenses and methods for manufacturing the same
US9377564B2 (en) 2011-04-15 2016-06-28 Qspex Technologies, Inc. Anti-reflective lenses and methods for manufacturing the same
US20130161844A1 (en) * 2011-12-27 2013-06-27 Norio TAKATORI Method for producing plastic lens
WO2016016808A1 (en) 2014-07-31 2016-02-04 Sabic Global Technologies B.V. Method of making plastic article
WO2016166619A1 (en) 2015-04-13 2016-10-20 Sabic Global Technologies, B.V. Photochromic spirooxazine compounds
US9522921B2 (en) 2015-04-13 2016-12-20 Sabic Global Technologies, B.V. Photochromic spirooxazine compounds

Also Published As

Publication number Publication date Type
DE69940232D1 (en) 2009-02-26 grant
EP0934968A3 (en) 1999-08-18 application
EP0934968B1 (en) 2009-01-07 grant
EP2025701A2 (en) 2009-02-18 application
CN1225928A (en) 1999-08-18 application
EP0934968A2 (en) 1999-08-11 application
EP2025701A3 (en) 2009-05-06 application
CN1198867C (en) 2005-04-27 grant
JPH11315199A (en) 1999-11-16 application

Similar Documents

Publication Publication Date Title
US5280070A (en) Polycarbonate-polymethyl methacrylate blends
US4474999A (en) Phenol compounds, process and polymers
US5010162A (en) Polycarbonate of alkyl cyclohexylidene bisphenol
US5034458A (en) Polycarbonates of substituted cyclohexylindenebisphenols
US3880783A (en) Transparent moulding composition of a polycarbonate and a resin
US6730720B2 (en) Method for reducing haze in a fire resistant polycarbonate composition
US4152367A (en) Branched polyaryl-sulphone/polycarbonate mixtures and their use for the production of extruded films
US6727303B2 (en) Flame retardant aromatic polycarbonate resin composition and molded articles thereof
US5869185A (en) Coatings useful for absorbing ultraviolet light
US4001184A (en) Process for preparing a branched polycarbonate
US4539370A (en) Thermoplastic moulding compositions
US6323291B1 (en) Compositions having low birefringence
EP0272417A2 (en) Blends of polycarbonate resins and polyester resins exhibiting improved color properties
US4902743A (en) Low gloss thermoplastic blends
CA2035149A1 (en) Blends of polycarbonates and aliphatic polyesters
WO2001005867A1 (en) Polycarbonate and molded polycarbonate articles
WO2002026862A1 (en) Use of copolycarbonates
JP2012116915A (en) Glass fiber-reinforced resin composition
JP2001323149A (en) Light diffusible aromatic polycarbonate resin composition
US5681905A (en) Gamma radiation-resistant blend of polycarbonate with polyester
US4748203A (en) Polymer mixture with PC and HIPS
JP2001214049A (en) Light-diffusing aromatic polycarbonate resin composition
US20030055200A1 (en) Plastic lens
JP2012153824A (en) Polycarbonate resin composition and molded article
US5491179A (en) Thermally stable, gamma radiation-resistant blend of polycarbonate with polyester

Legal Events

Date Code Title Description
AS Assignment

Owner name: GENERAL ELECTRIC COMPANY, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BROWN, MICHAEL W.;HAMILTON, DOUGLAS G.;MICHEL, RODNEY L.;AND OTHERS;REEL/FRAME:008978/0214;SIGNING DATES FROM 19980127 TO 19980130

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

AS Assignment

Owner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GENERAL ELECTRIC COMPANY;REEL/FRAME:020820/0578

Effective date: 20070831

AS Assignment

Owner name: CITIBANK, N.A., AS COLLATERAL AGENT, NEW YORK

Free format text: SECURITY AGREEMENT;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:021423/0001

Effective date: 20080307

Owner name: CITIBANK, N.A., AS COLLATERAL AGENT,NEW YORK

Free format text: SECURITY AGREEMENT;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:021423/0001

Effective date: 20080307

FPAY Fee payment

Year of fee payment: 12

AS Assignment

Owner name: SABIC INNOVATIVE PLASTICS IP B.V., NETHERLANDS

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:CITIBANK, N.A.;REEL/FRAME:032459/0798

Effective date: 20140312

AS Assignment

Owner name: SABIC GLOBAL TECHNOLOGIES B.V., NETHERLANDS

Free format text: CHANGE OF NAME;ASSIGNOR:SABIC INNOVATIVE PLASTICS IP B.V.;REEL/FRAME:038883/0906

Effective date: 20140402